2-(二硝基亚甲基)-4,5-咪唑烷二酮与甲醇的反应研究

Study on Reaction of 2-(Dinitromethylene)-4,5-imidazolidinedione with Methanol

以 2-甲基咪唑为原料合成 2-(二硝基亚甲基)-4,5-咪唑烷二酮(1), 收率为 33.9% (16.8%文献值), 首次采用低碳液态醇实现 1 的开环反应, 产物为 FOX-7. 对反应条件进行了优化, 对比了甲醇、甲酸、氨水三种亲核试剂的开环效果, 开环试剂为甲醇时, FOX-7 收率为 94.6%, 高于文献值(87.4%). 研究了 1 的络合性能, 合成了 1 的甲醇加合物 2 并进行了结构表征. 对开环反应机理和乙二酰脲的形成机理进行了探讨.

Low temperature nitration of 2-methylimidazole gave 2-(dinitromethylene)-4,5-imidazolidinedione (1) in 33.9% yield (16.8% in literature). Ring cleavage of 1 to FOX-7 was achieved by liquid alcohols for the first time and reaction conditions were optimized. The effect of methanol, formic acid and aqueous ammonia as nucleophiles on the ring cleavage of I was investigated. It was found that methanol was a better nucleophile than other alcohols with 94.6% yield of FOX-7 (87.4% in literature). Methanol adduct 2, the first adduct of 1, was synthesized and characterized. The reaction mechanisms of ring cleavage and parabanic acid formation were discussed.